JPH0463344A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the redeposition of coloring matters and dyes on the photosensitive material and to prevent the crystal precipitation to the wall surfaces of a processing tank and rollers by specifying the compsn. of a stabilizer. CONSTITUTION:The photosensitive material having >=80mol% average silver chloride ratio of a silver halide emulsion is subjected to imagewise exposing, then to color development processing followed by bleaching, fixing and stabilizing treatments. The photosensitive material is processed by incorporating a water-soluble surfactant into the stabilizer in such a manner as to have 15 to 60dyne/cm surface tension and bringing an ion exchange resin or adsorbent into contact with the material in a stabilizing bath. The compd. of formula I, etc., are preferably used as the surfactant. In the formula, R denotes an alkyl group, hydrogen atom, etc.; A and B denote the group of formula II; n1, m1 and l1 denote 0 to 3; D denotes hydrogen, -SO3H, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, it improves residual color stains, processing tanks, and crystal precipitation on rollers, and improves rapid processing and The present invention relates to a method for processing silver halide color photographic materials that enables low replenishment.

[Background of the invention]

Generally, in order to obtain a color image by processing an imagewise exposed silver halide color photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material), the metallic silver produced after the color development process is desilvered, and then washed with water. Treatment steps such as stabilization or water washing alternative stabilization are provided.

In the past, photosensitive materials were collected at a photo lab and processed in 24 to 48 hours from reception to finishing.However, as part of improving service to users, there is a demand for finishing within a few hours from reception, and recently minilabs have been With the spread of in-house processing equipment, it has become necessary for in-house processing to be completed within one hour from reception, and the development of rapid processing technology is becoming more and more urgent.

In response to this, a rapid process for color paper called Process RA-4 (developing time is 3 minutes, processing temperature is 35
°C, processing time breakdown: color development 45 seconds, bleach fixing 45 seconds
(consisting of 3 steps, 90 seconds and 90 seconds of stability) has also been proposed by Eastman Kodasoku Company.

Looking at the conventional technologies for these rapid processing, (1)
Techniques based on improvements in photosensitive materials, (2) Techniques based on physical means during development processing, (3)
Techniques that involve improving the composition of the processing solution used in development processing are broadly divided into: (1) Techniques for improving the composition of the processing solution used in development processing; (1) techniques for improving the composition of silver halide;
Examples include a technique for making silver halide fine grains as described in No. 223, and a technique for reducing silver bromide of silver halide as described in JP-A-58-18142 and JP-B-56-18939.

■ Use of additives, such as the technique of adding l-aryl-3-pyrazolidones having a specific structure to photosensitive materials as described in JP-A-56-64339, and JP-A-57-144.
No. 547, No. 58-50534, No. 58-50535
For example, there is a technique of adding l-arylpyrazolidones to a light-sensitive material as described in No. 58-50536.

■Technology using high-speed reactive couplers, for example
No. 10783, JP-A-50-123342, JP-A No. 51-
102,636 using a high speed yellow coupler.

■Regarding film thinning technology for photographic constituent layers, for example, JP-A No. 6
The technique for thinning photographic constituent layers described in No. 2-65040 can be mentioned.

Furthermore, regarding the above (2), there may be mentioned a processing liquid stirring technique, for example, a processing liquid stirring technique described in JP-A-62-180369.

Regarding (3) above, ■Technology that uses a development accelerator.

■ Techniques for enriching color developing agents ■ Techniques for reducing the concentration of halogen ions, especially bromide ions, etc. are known.

However, even if processing is performed using the above-mentioned rapid processing technology, if the processing time is short, residual color stains may occur due to insufficient elution of the sensitizing dye or anti-irradiation dye (AI dye) present in the light-sensitive material into the processing solution. is a problem. Furthermore, when using a water-washing alternative stabilization process, the storage stability of the white background was also a problem.

Conventionally, as a technique to solve this problem, there has been a technique to accelerate the elution of the sensitizing dye by adding a fluorescent brightener etc. to the stabilizing solution (for example, Japanese Patent Application Laid-Open No. 62-62359, etc.), or a bleaching type AI dye. Attempts have been made to erase the color of the dye by using a (color-erasing type) material and allowing sulfite ions to be present in the processing solution.

However, even if these methods are used, if the processing runs are controlled, the pigments and dyes eluted from the photosensitive material will accumulate in the processing solution, and the accumulated pigments and dyes will conversely stain the photosensitive material. This causes severe residual color staining, and furthermore, the pigments and dyes accumulated in the processing solution adhere to and precipitate on the processing tank and rollers. Such problems of eluted dyes and dyes re-dying onto light-sensitive materials and depositing on the walls of processing tanks and rollers are particularly likely to occur in the stabilizing bath of the final bath. Furthermore, as processing speeds up and replenishment rates become lower in recent years, these problems have become even more serious.

[Purpose of the invention]

In order to solve the above-mentioned problems, the purpose of the present invention is to prevent the precipitation of crystals on the color paper stain treatment tanks and rollers that occur during processing, and to improve halogenation, which enables rapid processing and low replenishment. An object of the present invention is to provide a method for processing silver color photographic materials.

Other purposes will become apparent in the description below.

[Structure of the invention]

The above-mentioned object of the present invention is to subject a silver halide color photographic light-sensitive material coated on a support and having an average silver chloride ratio of 80 mol% or more to color development after imagewise exposure.
In a processing method in which bleaching treatment, fixing treatment and stabilization treatment are subsequently performed, the surface tension of the stabilizing solution is 15 to 60 dyne.
A method for processing a silver halide color photographic light-sensitive material, which comprises containing a water-soluble surfactant in a stabilizing solution so that /am, and bringing an ion exchange resin or an adsorbent into contact with the stabilizing bath. achieved.

In addition, as a preferable embodiment of the present invention, the water-soluble surfactant is the following - Shipura [1) or - Shipura [...],
On the support J: A silver halide color photographic light-sensitive material in which the silver halide emulsion coated has an average silver iodide ratio of 2 mol% or more, and the silver halide emulsion coated on the support has a silver chloride ratio of 2 mol % or more. In a method in which a silver halide color photographic light-sensitive material containing 80 mol% or more is mixed and processed using at least one same replenisher in a processing bath excluding a color developing bath, the former silver halide color photographic light-sensitive material is A preferred embodiment is a processing method characterized in that part or all of the overflow liquid is passed into a stabilizing bath in which the material is processed.

General formula [1] R-0-(A tod (B) In the formula, R represents a hydrogen atom in a straight chain or branched chain having 4 to 25 carbon atoms. (However, R1 and R3 are each a hydrogen atom. or represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a represents an integer of O to 4.) n and m each represent O or an integer of 1 to 200, but at the same time O It won't happen.

A and B are respectively H , and may be the same or different.

(However, nl, m, and L each represent 0.l, 2, or 3, but n, ml, and Ql are not 20 at the same time.) D is a hydrogen atom, -5O, H, or -PO, Represents H.

M here represents a hydrogen atom, an alkali metal or ammonium.

Shipura (n) In the formula, R5 is a hydrogen atom, a hydroxy group, or a lower alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl, etc.). and R6 and R6 may be the same or different, respectively.

121 to Q each represent an integer of 0 or 1 to 4, p
l Q+ and q2 each represent an integer of 1 to 15.

The present invention will be explained in detail below.

As mentioned above, in the conventional method for dealing with residual color staining, the accumulated pigments and dyes are redeposited due to running, so in the present invention, a water-soluble surfactant is added to the stabilizing bath where staining is particularly likely to occur. By adding a sensitizing agent, the elution of sensitizing dyes with poor hydrophilicity is promoted, and furthermore, the ion exchange resin or adsorbent is used in the stabilizing bath to remove the pigments and dyes that accumulate in the stabilizing solution. An attempt was made to prevent re-dying of the material and crystal precipitation on the processing tank walls and rollers.

As a result, it has become possible to significantly prevent residual color staining even in rapid processing and low replenishment systems, and it has also become possible to prevent pigments and dyes accumulated in the stabilizing bath from depositing on the roller tank wall.

In addition, by applying the processing method of the present invention to an automatic developing machine for common processing of color negatives and paper, which is designed to be compact and cost-reduced by sharing replenishment tanks, pumps, etc., paper, residual color stain, and stabilization bath roller
Prevention of precipitation on tank walls was confirmed.

Next, specific exemplary compounds for general formula [I] and -Funazo (II) will be listed, but the present invention is not limited thereto.

(Exemplary compound) ■ ] C+2HzsO(C2H+O)+. H ■ CaH++O(C+HaO)+sH ■ CIH+ 5o(CJtO)+5OxNa■ C+2HzsO(CJtO)+1P()+Naz■ ■ rI.

■ ■-13 ■ Hosen CHCH, 0±-shi鉗, CH, 0ner HCH.

(CHz)+S’ CH.

OSi　O5i(CHz)s c, Hf　0CJt　+H (CHl)+5i CH.

0 + S i -0±5i(CHs)sCsHfv
OCJ< Un0-5+(CHs)+CHyu(CHz)ss+-0+ Si O75i(CL)x
C+HiOCJt)+-5i(CHi)+(CHz)+
5l CH.

0 + Sr-0+25+(CHx)+C,H 0C2
J) 1oSl(CJil)+(C)lx)+5i CO.

OSi　O5i(CJ)3 CsHtfOCJ+-900, H.

(Exemplary compound) t-1 CH5 (CH3)3Si-0-5i-0-5i(01,).

C5Hk　0C2H4HoO1l t-2 CHl ■ CH.

(C)+1)IsI O+ Sr-〇:hs” (c
Hl ) yC, HreOC2H, -10cH1 ■ CH.

(CH,)+Si -0-5i -0-Si(CH,)
.

C) HfOC2Ht) 1o 5l (CHz:h■ CH.

(CH,), Si -0-5i-○-5i (CH5)+
C+Hf0CJ, -COCH.

■ CHs CHh CH, -5i-0'-5i (CHz) + (OCR+CH
)+(OCH2C1h), OCH+CH, CH, CH.

■ CH, CH.

CH.

■ ■ CH.

C) lyu CH.

CH.

lt-15 11I-1 (QC, HυTeoc, H, +0CHsIon exchange resins or adsorbents used in the present invention include Diaion manufactured by Mitsubishi Chemical Industries, Amberlite manufactured by Organo, Duolite manufactured by Sumitomo Chemical, Sumikaion, It is commercially available under various names such as Sumikylate and Unicerec manufactured by Unitika.

Among the ion exchange resins of the present invention, ion exchange resins with particularly preferable effects of the present invention are anion exchange resins, and specific examples of chemical structures thereof include the following H and CCH.

Commercially available products Mitsubishi Diaion SA-10A, SA-1
1A.

PA=308 l-2 Commercially available product/Mitsubishi Diaion 5A 2OA, SA-21A.

PA-408 [1-3 [R in the formula: hydrogen atom, NCR')! or a lower alkyl group (where R' is a hydrogen atom or a lower alkyl group, except when both are hydrogen atoms), n; an integer of O to 3] Commercial products: Mitsubishi Diaion WA-10, WA-11 (n
; l~3) Commercial product: Mitsubishi Diaion WA-30 The anion substitutes of these basic ion exchange resins include, but are not limited to, OH-, Cl2-, SO, "-
Br-C00H-, CO3''-, So,'- are preferred.

I[1-6 I[1-4 (n; 0 to l) Commercial product, Mitsubishi Diaion WA-20, WA-21x:
y-33:67 x:y-30 near 0 CI! H2 & x:y-10:90 I[1-10 CHl CH.

H C=〇 1←C-CH2→- CH.

x: y)1cO, e20: 80 C=0 -(-CHCH,→- : z=10:10:7
Near 3ll-16 C,. + (2゜

C=O CQ0 y:z-10:90 CI2θ CI2° CQo x: z,: z=-10:15 near 5CQ”
C11° ,,,"in, 71'1 Q0CQ0 x : Z+ : z2=IO:20 near 0CQθ
CQe x: Z,: z2=15:15 near 0CQθ
CQo x : z, : z2=5 :25 near 0 In the present invention, the following adsorbent substances can also be used.

[Contact substance]

(a) Activated carbon (b) Clay material (c) Polyamide polymer compound (d) Polyurethane polymer compound (e) Phenol resin (f) Epoxy resin (g) Polymer compound having hydrazide group (h) Polytetra Polymer compound containing fluoroethylene (1) Monohydric or polyhydric alcohol methacrylic acid monoester-polyhydric alcohol methacrylic acid polyester copolymer The activated carbon (a) in the substance of the present invention refers to any activated carbon that has adsorption ability. Good too. Raw materials for activated carbon include wood, sawdust, coconut shell, lignin, cow bone, blood, lignite,
Any material such as charcoal, peat, or coal may be used. There are powder activated carbon and granular activated carbon in terms of form, but the present invention may use either of them. To produce powdered activated carbon,
After pulverizing the raw materials, activation is performed by carbonizing them under high heat.

In some cases, activation may be performed by passing water vapor under high heat, or by soaking in a solution of zinc chloride, phosphoric acid, sulfuric acid, alkali, etc., followed by firing and carbonization. There is also a method of oxidizing and activating a portion of the charcoal by igniting it under local pressure or heating it in air, carbon dioxide, or chlorine gas. Activated products are usually washed to remove ash and chemicals.
It is crushed and dried to produce powdered activated carbon. Powdered activated carbon is made by forming crushed charcoal powder into a certain powder size using tar, pitch, etc. as a binder, drying and sintering it, and then activating it. Furthermore, when coconut shells or coal are used, they are crushed, sieved, and then carbonized and activated under high heat to obtain granular activated carbon. In the present invention, powdered or granular activated carbon can be used regardless of the raw material and activation method, preferably granular activated carbon, particularly preferably coconut shell activated carbon and activated carbon with molecular sieving ability. It has slit-like pores, and the pore size is preferably 6 Å or more and the width is 15 Å or less. Activated carbon having such molecular sieving ability is disclosed in Japanese Patent Application Laid-Open No. 58-14831 by the present applicant.
The contents of the publication may be referred to.

The clay material (b) in the material of the present invention is an inorganic material that contains silica and alumina as essential components and may contain other components as necessary, such as silica gel, bentonite, activated clay, acid clay, kaolin, zeolite, etc. It includes seven stone groups, etc. Bentonite is a clay acid based on hydrous aluminum silicate whose main ore is montmorillonite. Activated clay is a clay material whose main ores are montmorillonite and hallosite. Acid clay is a similar clay material. Kaolin is a clay material consisting of naturally hydrated aluminum silicate. Fluorite groups such as zeolites are natural or synthetic fluorites, and are clay materials that have uniform pore diameters and exhibit molecular/absorbing action. Examples of materials other than zeolite include nudafluorite and chabasite.

The polyamide-based polymer compound (c) in the substance of the present invention is a polymer having an acid amide bond such as 6-nylon, 6.6-nylon, 6.10-nylon.

The polyurethane-based polymer compound (a) in the substance of the present invention has urethane bonds -NHCO in the repeating unit of the main chain.
It is a polymer compound with O-.

The phenolic resin (e) in the substance of the present invention is a resin obtained from phenols such as phenol, cresol, xy/lenol, and resorcin and aldehydes such as formaldehyde, acetaldehyde, and furfural, and modified resins thereof. It is a phenol formaldehyde resin, and commercially available products include, for example, Duolite S-761 resin manufactured by Sumitomo Chemical Co., Ltd.

The polymer compound having a hydrazide group (g) in the substance of the present invention is, for example, a sulfohydrazide group, a carbonylhydrazide group, or a hydrazide group added to a methyl acrylate-divinylbenzene copolymer, a styrene-divinylbenzene copolymer, etc. It is a high-molecular compound.

The polytetrafluoroethylene-containing polymer compound (h) in the substance of the present invention is a mixture of polyethylene, polypropylene, polyvinyl chloride, etc. and polytetrafluoroethylene or pure polytetrafluoroethylene, preferably polytetrafluoroethylene. The content of ethylene is 50% or more.

The monohydric or polyhydric alcohol methacrylic acid monoester that is the monohydric or polyhydric alcohol methacrylic acid monoester-polyhydric alcohol methacrylic acid polyester copolymer component (1) in the substance of the present invention may be any ivy acrylate copolymer. Although it may be a polymer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-hydroxy-ethyl methacrylate, 2-hydroxy-propyl methacrylate and the like are preferred. As the polyhydric alcohol methacrylic acid polyester as a crosslinking monomer, ethyl glycol dimethacrylate-1 is most preferred, and polyethylene glycol (n-1 to 10) dimethacrylates such as diethylene glycol dimethacrylate and triethylene glycol dimethacrylate are preferred. is also preferable. Furthermore, trimethylolglopane trimethacrylate, pentaerythritol tetramethacrylate, etc. can also be used. Preferably, the porous methacrylate copolymer is a monohydric or polyhydric alcohol methacrylic acid monoester 10 to 9
A composition having a composition of 41% is used. Among these, those containing 50% or less of polyhydric alcohol tamacrylic acid polyester are preferred. Specifically, Amberlite XDA-7, 8, and 9 manufactured by Rohm and Haas Co., Ltd. are preferred.

In addition, these materials of the present invention are preferably porous with a large surface condition, and have a specific surface area of about 1 to 3000 m''/g.
It is preferable that the concavity is within the range of 100 to 1000 m, more preferably
It has a specific surface area of "/g" and a pore radius of 4 to 2,000 pores.

In the present invention, the color developing solution used in the color development step is replaced with hydroxylamine, which is conventionally used as a preservative.
No. 146042, No. 63-146041, No. 63-1
No. 46040, No. 63-135938, No. 63-11
Hydroxylamine derivatives described in No. 8748 and hydroxamic acids, hydrazines, hydrazides, phenols, σ-hydroxyketones, σ-aminoketones, sugars, monoamines, diamines, quaternary described in JP-A No. 64-62639 Ammonium salts, nitroxy radicals, alcohols, oximes, diazide compounds, fused cyclic amines and the like are preferably used as the organic preservative. In particular, it is preferable to contain the compound shown in the following - Funagura (TV) in order to achieve the effects of the present invention.

General formula [■] Each represents an alkyl group or a hydrogen atom that is not an elementary atom, and the alkyl groups represented by R1 and R7 may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. The alkyl groups of R1 and R1 include those having substituents, and R1 and R3 may be combined to form a ring, for example, a heterocyclic ring such as piperidine or morpholine.

Specific compounds of the hydroxylamine-based compounds represented by -shipped CrV) are described in U.S. Patent No. 3,287,125, U.S. Pat. Particularly preferred specific exemplary compounds are shown below, where R1 and R1 each represent an alkyl group or a hydrogen atom. However, both R and R8 are not hydrogen atoms at the same time. Further, R3 and R may form a ring.

In the general formula (IV), R1 and R2 are simultaneously water, and these compounds are usually free amines, hydrochlorides, sulfates, p
-Used in the form of toluenesulfonate, oxalate, phosphate, acetate, etc.

The concentration of the compound represented by the general formula [■] in the color developing solution is generally 0.2 g/12-50 g IQ, preferably 0.5 g #1-30 g/12. More preferably 1g/1
It is 5gI2.

In addition, the compound shown in -Funazo [■] can be used in combination with conventionally used hydroxylamine and organic preservatives, but it is preferable not to use hydroxylamine because it improves developability. preferable.

When the color developing solution contains the compound shown in the following - ship stock ['l], it shows an improvement effect on the air oxidation of the color developing solution, and even if mixed into the bleach-fixing solution, there is almost no adverse effect. It is preferably used because it does not give any

In the formula, R1 is a hydroxyalkyl group having 2 to 6 carbon atoms,
R22 and R23 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyl formula having 2 to 6 carbon atoms; X' and Y' each represent a hydrogen atom; It represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.

Preferred specific examples of the compound represented by -Funazo (V) are as follows.

(V-1) Ethanolamine (V-2) Jetanolamine (V-3)) Ethanolamine (V-4) Di-isopropanolamine (V-5) 2-
Methylaminoethanol (v-6) 2-ethylaminoethanol (V-7) 2-dimethylaminoethanol (V
-8) 2-diethylaminoethanol (V-9) l-diethylamino-2-propanol (V-10) l-diethylamine-1-propanol (V-11) 3-dimethylamino-1-propanol (V - 12) Isopropylaminoethanol (V-13) 3-amino-1-propanol (V-14) 2-amino-2-methyl-1,3
-propazinol (v -15) ethylenediaminetetraisoprobanol (v -16) benzyljetanolamine (v -1
7) 2-7mi/-2-(human o xy) chill)-1
, 3-propazinol The compound represented by the above-shipped CV] is preferably used in the range of 1 g to 100 g per 1ff of color developer, more preferably in the range of 2 g to 30 g, from the viewpoint of preventing air oxidation. used.

The color developing agent used in the color developer is preferably a p-phinidine diamine compound having a water-soluble group. The water-soluble group has at least one on the amino group or benzane nucleus of the p-7-nylene diamine compound, and a specific example of the water-soluble group is (CHs)n CHzOH.

(CHRII NH5I:h (C4)n CHs.

-(cHz)m-0-(CH=)n-CHs-(CH2
CH2O)ncmH*m++ (m and n are each 0
Represents an integer greater than or equal to ), -COOH group, -SO, H group, etc. are mentioned as preferable ones.

Examples of color developing agents that are preferably used are shown below.

[Example color developing agent]

Among the above-mentioned exemplified color developing agents, exemplified No.
, (CD-1), (CD-2), (CD-3), (C
D-4), (CD-6), (CD-7) and (CD-
15), particularly preferably N. .

(CD-1).

The above color developing agents are usually hydrochloride, sulfate, 1. .

It is used in the form of salts such as toluene sulfonate.

The amount of the preferably used p-phenylenediamine compound added is preferably 0.5 x 10-'' mol or more per color developer iff, more preferably 1.
10-" to 1.OX 10-' moles, most preferably 1.5X 10-' to 7.OX 10-"
It should be in the molar range.

The sulfite concentration in the color developer is 1. Even in a low concentration range of OX 10-'' moles or less, and even in a low concentration range of 5.OX 10-'' or less, staining and precipitation in the stabilizing solution can be prevented.

The color developer may contain the following developer components in addition to the above components.

Alkaline agents such as sodium hydroxide, potassium hydroxide, silicates, sodium metaborate, potassium metaborate,
Trisodium phosphate, tripotassium phosphate, borax, etc. can be used alone or in combination as long as no precipitation occurs and the pH stabilizing effect is maintained. Furthermore, due to pharmaceutical needs or for the purpose of increasing ionic strength, disodium hydrogen phosphate, dipotassium hydrogen phosphate,
Sodium bicarbonate! Various salts such as potassium carbonate and i-acid salts can be used.

Additionally, inorganic and organic antifoggants can be added as necessary.

Furthermore, a development accelerator may also be used if necessary. As a development accelerator, U.S. Pat.
No. 04, No. 3,671,247, Special Publication No. 44-950
Various pyridinium compounds as typified by Publication No. 3, other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate, and U.S. Pat.
, No. 533,990, No. 2,531.832, No. 2.
No. 950970, No. 2.577127 and Special Publication No. 1977
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc., described in Japanese Patent No. 9504, 7-enethyl alcohol described in U.S. Pat. No. 2,304,925, as well as acetylene glycol, methyl ethyl ketone, cyclohexanone, Examples include thioethers, pyridine, ammonia, hydrazine, and amines.

Benzyl alcohol is not preferred for use in the present invention;
In addition, it is preferable to eliminate the use of poorly soluble organic solvents such as the above-mentioned phenethyl alcohol. Its use is due to the long-term use of color developing solution.
In particular, tar is likely to be generated during running processing using a low replenishment method, and such tar may adhere to the vapor photosensitive material to be processed, resulting in a serious failure that significantly impairs its commercial value. In addition, since poorly soluble organic solvents have poor solubility in water, not only is it troublesome that a stirring device is required to prepare the color developing solution itself, but the use of such a stirring device also reduces the dissolution rate. Due to its poor performance, there is a limit to its development accelerating effect. Furthermore, poorly soluble organic solvents have high biochemical oxygen demand (BOD), etc., and cannot be disposed of as they are in sewers, rivers, etc., and require waste liquid treatment. However, there are problems such as the large amount of labor and expense required to treat the waste liquid, so it is necessary to reduce or eliminate the amount of not only benzyl alcohol but also other poorly soluble organic solvents used. is preferred.

The color developing solution may contain a fluorescent whitening agent represented by the above-mentioned general formula [2-1].

Furthermore, the color developing solution may contain ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other compounds described in Japanese Patent Publications Nos. 47-33378 and 44-9509, if necessary. It can be used as an organic solvent to increase the solubility of the main drug.

Furthermore, an auxiliary developer may be used with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminephenol sulfate, (methol)
, phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N', N'-tetramethyl-2=
722 diamine hydrochloride and the like are known, and the amount added thereof is usually preferably 0.01 g to 1.0 g/(l).

Furthermore, various other additives such as anti-staining agents, anti-sludge agents, interlayer effect promoters, etc. can be used.

In addition, for the color developing solution, if necessary, the above-mentioned
A chelating agent represented by the general formula K-XV) may be added.

Each component of the color developing solution can be adjusted by sequentially adding and stirring the components to the same amount of water. In this case, components with low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, multiple components that can coexist stably are prepared in a concentrated aqueous solution,
Or, add the pre-prepared solid state to a small container into water and stir. ! 1. A color developing solution can be obtained.

The color developing solution can be used at any pH*, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0.
More preferably, it is used at a pH of 9.8 to 12.0.

The processing temperature with the color developer is generally 30°C or higher, preferably 33°C or higher, particularly preferably 35°C to 65°C, and the processing time is preferably 90 seconds or less, more preferably 3 seconds or more and 60 seconds or less. The time is particularly preferably 3 seconds or more and 45 seconds or less.

In the present invention, since the effect of the present invention is well exhibited when the replenishment is low, the replenishment amount of the color developer is preferably 20 to 150+o (2/m" or less, more preferably 30 to 120+++ff/■ If it is 8, it will be effective against Stin.

In color development processing, there are various methods including bath processing, such as a spray method in which the processing solution is atomized,
Alternatively, various processing methods such as a web method involving contact with a carrier impregnated with a processing solution, or a developing method using a viscous processing solution may be used.

The bleaching agents used in the bleaching solution in the present invention are the ferric complex salts of organic acids represented by the following (A-1) or CB-I) and the following A'-1 to A'-1 to 8''-16, etc. Examples include ferric complex salts of exemplified compounds, but preferred are vg2 iron complex salts of organic acids represented by the following -Funakura [A-I] or CB-1].

-Ship stock (A-I) In the general formula [:A-I), A and ~A may be the same or different, respectively, -CH, OH, -C00M
or -POsM, M, where M, M, and M are hydrogen atoms, alkali metal atoms (e.g., sodium,
potassium) or ammonium group.

X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, propylene, butylene, pentamethylene, etc.). Examples of the substituent include a hydrogen group and an alkyl group having 1 to 3 carbon atoms.

Below, the compound (-
) (AI l ) (AI6) (A, -2) 0M (AI-7) (A, -3) (AI4) (A, -9) (AI C■.

(A, -10) (A, -11) As the ferric complex salts of the compounds (All) to (A, -12), any sodium salt, potassium salt or ammonium salt of these ferric complex salts may be used. It can be used for.

Among the above compound examples, those particularly preferably used in the present invention are (A, -1), (A, -3), (A,
-4), (AI-5), and (AI-9), and particularly preferred is (All).

General formula (B-1) has the same meaning, and n represents an integer of 1 to 8. B1 and B may be the same or different, and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms (eg, ethylene, propylene, butylene, pentamethylene, etc.). Examples of the substituent include a hydroxyl group, a lower alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group), and the like.

Preferred specific examples of the compound represented by the general formula CB-1) are shown below.

(B, -1) (B, -2) (B, -3) (B□-4) In general stock CB-I), A1 to A are the above and (B1
6) (B+7) The ferric chain salts of these compounds (B1-1) to (B, to 7) may optionally be sodium salts, potassium salts, or ammonium salts of ferric complex salts of these compounds. can.

In the present invention, the above - shipyard (A-I) or [B-1]
In view of the sufficiently high oxidizing power of the ferric complex salt of the organic acid shown in This is a preferred embodiment for carrying out the invention.

Among the above compound examples, those particularly preferably used in the present invention are CB+-1), (B12), (B,
-7), particularly preferred is (B, -1)
It is.

The amount of organic acid ferric complex salt added is 0.1 to 112% of bleaching solution.
It is preferably contained in a range of 2.0 mol, more preferably in a range of 0.15 to 1.5 mol/Q.

Examples of preferable bleaching agents other than the compounds shown in - Shipura (A-I) or CB-I) include ferric complex salts of the following compounds (e.g. salts of ammonium, sodium, potassium, triethanolamine, etc.) but not limited to these.

(A″-1) Ethylenediaminetetraacetic acid (A′-2) Trans-1,2-cyclohexanediaminetetraacetic acid (A′-3) Citroxyethylglycinate (A′-
4) Ethylenediaminetetrakismethylenephosphonic acid (A'-5) Nitrilotrismethylenephosphonic acid (
A'-6) Diethylenetriaminepentakismethylenephosphonic acid (A'-7) Diethylenetriaminepentaacetic acid (A'-
8) Ethylenediaminediorthohydroxyphenylacetic acid (A'-9) Hydroxyethylethylenediaminetriacetic acid (A'-10) Ethylenediaminedipropionic acid (
A''-11) Ethylenediamine diacetic acid (A'-
12) Hydroxybutyliminodiacetic acid (A'
-13) Nitrirotriacetic acid (A'-
14) Nitrilotripropionic acid (A'-15)
Triethylenetetraminehexaacetic acid (A'-16) Ethylenediaminetetrapropionic acid bleaching solution contains
1 of the ferric complex salt of the compound of A'1-A''-16 to the ferric complex salt of the compound represented by A-I) or CB-■]
A species or a combination of two or more species can be used.

When using two or more organic acid ferric complex salts in combination, the above-mentioned -
The second of the compounds represented by Shipura (A-1) or CB-I)
It is preferable that the iron complex salt accounts for 70% or more (in terms of mole), more preferably 80% or more, particularly preferably 9
It is 0% or more, most preferably 95% or more.

In addition, from the viewpoint of speed, ammonium is preferable as a cation in the bleaching solution, but as mentioned above,
Or, since the ferric complex salt of an organic acid represented by CB-1'l has high oxidizing power, it is possible to use an amine salt other than ammonium such as potassium, sodium, alkanolamine, etc., and in a preferred embodiment. be. In this case, the ammonium salt is less than 50 mol% of the total cations, preferably 2
The content is preferably 0 mol%, particularly preferably 10 mol% or less, in order to achieve the above effects.

Organic acid iron(I[I) complex salts may be used in the form of complex salts, or iron(n[) salts such as ferric sulfate, ferric chloride, ferric acetate, ferric ammonium sulfate, Iron (
III) Ionic complex salts may be formed. When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. Furthermore, when forming a complex salt in a solution using a ferric salt and an aminopolycarboxylic acid, one or more types of ferric salts may be used.

Furthermore, one type or two or more types of aminopolycarboxylic acids may be used. In any case, the aminopolycarboxylic acid may be used in excess of the amount needed to form the iron (I[I) ion complex salt.

Further, the above-mentioned bleach-fix solution or bleaching solution containing the iron (I[I) ion complex may contain metal ion complex salts other than iron, such as cobalt, copper, nickel, and zinc.

The bleaching solution contains imidazole and its derivatives described in Japanese Patent Application No. 63-48931, or compounds represented by general formulas [I] to [■] described in the same specification, and at least one of these exemplary compounds. By doing so, the effect on speed can be reduced.

In addition to the bleaching accelerators mentioned above, the exemplified compounds described on pages 51 to 115 of Japanese Patent Application No. 60-263568 and pages 22 to 25 of Japanese Patent Application Publication No. 17445/1982
The exemplified compounds described in JP-A-53-95630 and JP-A-53-28426 can also be used in the same manner.

These bleach accelerators may be used alone or in combination of two or more, and the amount added is generally about 0 per 1a of bleaching solution.
．． The range is preferably 01-100g, more preferably 0
．． 05 to 50g, particularly preferably 0.05 to 15g
It is g.

When adding a bleach accelerator, it may be added and dissolved as is, but it is common to dissolve it in water, alkali, organic acid, etc. before adding it, and if necessary, add methanol, ethanol, ascent, etc. It can also be added after being dissolved in an organic solvent.

The temperature of the bleaching solution is preferably 20°C to 50°C, preferably 25°C to 45°C.

The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less.

Note that the pH of the bleaching solution is the pH of a processing tank for processing silver halide photosensitive materials, and can be clearly distinguished from the pH of a so-called replenisher.

Halides such as ammonium bromide, potassium bromide, and sodium bromide are usually added to the bleaching solution. Further, various optical brighteners, antifoaming agents, or surfactants can be contained.

The preferred replenishment amount of bleaching solution is 1 m of silver halide color photographic light-sensitive material! 500m12 or less, preferably 2
The range is from 0mff to 400rn(l), most preferably from 40mQ to 350m12, and the lower the replenishment amount, the more pronounced the effect of the present invention.

In the present invention, in order to increase the activity of the bleaching solution, air or oxygen may be blown into the processing bath and the processing replenisher storage tank, if desired, or a suitable oxidizing agent such as hydrogen peroxide, Bromates, perfIL salts, etc. may be added as appropriate.

Next, as described above, the fixing agent used in the fixing solution in the fixing step adopted after the bleaching step is at least 0.
Although 2 mol/a of thiosulfate is used, the mixed use of thiocyanate can improve the problem of drip failure, which is a problem of the present invention.

The amount of thiocyanate added is 0.1 to 3.0 mol/
Q is preferable, more preferably 0.2 to 2.5 mol/Q
is within the range of

In addition to these fixing agents, the fixing solution also contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,
It may contain one or more types of pH buffering agents consisting of various salts such as sodium acetate and ammonium hydroxide.

Furthermore, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, or ammonium bromide. Also borates, oxalates, acetates, carbonates,
Compounds known to be added to normal fixing solutions, such as pH buffering agents such as phosphates, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, in the fixing solution of the present invention, ammonium ions are present at 50 mol % or less, preferably 20 mol % or less, particularly preferably 0 to 10 mol % of the total cations, which prevent staining when the fixing solution is directly processed from the bleaching solution. This is a preferred embodiment because it is possible to reduce ammonium ions and to reduce pollution by reducing ammonium ions, but since reducing ammonium ions may affect fixing properties, it is preferable to reduce the amount of thiocyanate to 0. 1 to 3.0 mol/Q or more, or the concentration of thiosulfate is 0.5 mol/Q or more, preferably 1.0 mol/Q or more, particularly preferably 1.0 mol/Q or more.
A preferred embodiment is 2 to 2.5 mol/Q.

Incidentally, silver may be recovered from the fixer by a known method. For example, electrolysis method (described in French Patent No. 2,299.667), precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, German Patent No. 2,331.220), ion exchange method (described in German Patent No. 2,331.220), Described in JP-A-51-17114, German patent 2,
548°237) and the metal substitution method (described in British Patent No. 1,353.805), etc. can be effectively used.

It is particularly preferable to recover silver from the tank solution in-line using an electrolytic method or an anion-exchange resin, as this improves suitability for rapid processing, but it is also possible to recover silver from the overflow waste solution and reuse it. .

The amount of replenishment of the fixer is preferably 1200 mQ or less per 1 m of photosensitive material, more preferably 2 mQ per 1 m of photosensitive material.
0 to 1000 mg, particularly preferably 50 to 800 mg
It is IIIQ.

The pH of the fixer is preferably in the range of 4 to 8.

A compound represented by the general formula (FA) described on page 56 of Japanese Patent Application No. 63-48931 and exemplified compounds thereof may be added to the fixing solution, and using a bleach-fixing solution or a fixing solution, Another effect can be obtained in that very little sludge is generated when processing a small amount of light-sensitive material over a long period of time.

The compound represented by the general formula (FA) described in the same specification is described in U.S. Patent No. 3,335,161 and U.S. Patent No. 3.2.
It can be synthesized by a general method as described in US Pat. No. 60,718. These compounds represented by the general formula (FA:) may be used alone or in combination of two or more.

Further, good results can be obtained when the amount of the compound represented by the general formula (FA) added is in the range of 0.1 to 200 g per 1Q of treatment liquid.

Sulfites and sulfite-releasing compounds may be used in the fixer. Specific examples of these compounds include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, and the like. Furthermore, the general formula C described on page 60 of the specification of Japanese Patent Application No. 63-48931
Compounds represented by B-13 or CB-2) are also included.

These sulfites and sulfite-releasing compounds are used in fixer lQ
At least 0.1 mol of sub-illEwi ions is required per unit, preferably in the range of 0.12 to 0.65 mol/Q, particularly preferably in the range of 0.15 to 0.50 mol/Q. Particularly preferred is a range of 0.120 to 0.40 mol/ρ.

The processing time with the bleaching solution and the fixing solution according to the present invention is arbitrary, but each is preferably 4 minutes 30 seconds or less, more preferably 20 seconds to 3 minutes 20 seconds, particularly preferably 40 seconds or less.
It is in the range of seconds to 3 minutes, particularly preferably 60 seconds to 2 minutes and 40 seconds.

In the processing method of the present invention, it is preferable as an embodiment of the present invention that the bleaching solution and the fixing solution are forcibly stirred. The reason for this is not only to better achieve the desired effects of the present invention, but also from the viewpoint of suitability for rapid processing. Forced liquid stirring here means forcibly stirring the liquid by adding a stirring means, instead of the usual diffusion movement of the liquid. As the forced stirring means, the means described in Japanese Patent Application No. 63-48930 and Japanese Patent Application Laid-open No. 1-206343 can be adopted.

In addition, in the present invention, the cross-over time between the color developing tank and the bleaching tank is within 10 seconds, preferably within 7 seconds, which is effective against bleaching blade blur, which is a different effect from the present invention. In order to achieve the effects of the present invention by installing a duckhill valve or the like to reduce the amount of processing liquid brought in by the photosensitive material, it is preferable that the stabilizing liquid contains sulfite. The sulfite may be any organic or inorganic substance as long as it releases sulfite ions,
Inorganic salts are preferred. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, and hydrosulfide. The above sulfite is in the stabilizing solution I
It is preferable that the amount is added such that at least 1 x 10-'' mol/Q is added, more preferably 5 x
It is added in an amount such that 10-' mol zl-10-' mol/Q, and it has the effect of the present invention, especially the effect of preventing stain, and is preferably employed in the third embodiment of the present invention. Ru. Although it may be added directly to the stabilizing solution, it is preferable to add it to the stable replenisher.

Particularly desirable compounds to add to the stabilizing solution include ammonium compounds. These are supplied by ammonium salts of various inorganic compounds, including ammonium hydroxide, ammonium bromide, 8M ammonium, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, and ammonium chloride, acidic ammonium heptadide, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate,
Ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium lauric tricarboxylate, ammonium benzoate, ammonium carbamate,
Ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate,
Ammonium sulfite, ethylenediaminetetraacetate [ammonium, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium hyfurinate, ammonium picridine dithiocarbamate, ammonium salicylate, succinate ammonium acid, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,
4.6-dolinitrophenolammonium and the like.

These may be used alone or in combination of two or more.

The amount of ammonium compound added is 0.00 per stabilizer IQ.
The range is preferably from 1 mol to LO mol, more preferably 0
．． The range is from 0.002 to 2.0 moles.

It is particularly preferred for the purpose of the present invention that the stabilizing liquid contains a chelating agent having a chelate stability constant of 8 or more for iron ions. Here is the chelate stability constant:
Written by L, G, Si l1en-A, E, Martell;
”5tability Con5tants of M
e-tal-4on CompIexes, Th
e Chemical 5ociety, Londo
n (1964).

S, Chaberek 1A, E, MarLe]l,
” Organic Sequestering Ag
ents'', a constant commonly known by Wiley (1959) and others.

Examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds.

Note that the above-mentioned iron ion means ferric ion (Fe').

Specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds. Namely, ethylenediaminediorthohydroquinephenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediamineniprobionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, ditrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonethane- 2-carboxylic acid, 2-phosphonobutane-1,24-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-)licarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, tetra Examples include sodium polyphosphate and sodium hexametaphosphate, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1
-diphosphonic acid, among which l-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The amount of the above chelating agent used is 0.01 to 5 per stabilizer IQ.
0 g is preferred, and more preferably a range of 0.05 to 20 g provides good results.

Other commonly known compounds that can be added to the stabilizer include polyvinylpyrrolidone (PVPK-15, K
-30, K-90), organic acid salts (citric acid, acetic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphates, borates, hydrochloric acid, sulfuric acid, etc.), antifungal agents ( Phenol derivatives, Carafur derivatives, imidazole derivatives, triazole derivatives, thiabendazole derivatives, organic halogen compounds, other fungicides known as slime control agents in the paper and pulp industry), optical brighteners, surfactants, Preservative, B+, Mg, Zns L
, i, Sn, TI% Zr, and other metal salts, but these compounds are necessary to maintain the pH of the stabilizing bath and do not have an adverse effect on the stability of color photographic images during storage and the occurrence of precipitation. Any compound may be used in any combination as long as there is no problem.

The processing temperature during stabilization treatment is 15°C to 70°c1
Preferably, the temperature is in the range of 20°C to 55°C. Further, the treatment time is preferably 120 seconds or less, more preferably 3 seconds to 90 seconds, and most preferably 6 seconds to 50 seconds, thereby achieving the effects of the present invention more effectively.

After the stabilization treatment, no water rinsing treatment is required, but rinsing with a small amount of water in a very short time, surface cleaning, etc. can be optionally performed as necessary. It is preferable that a soluble iron salt be present in the stabilizing solution in order to achieve the effects of the present invention. Examples of the soluble iron salt include ferric chloride, ferrous chloride, ferric phosphate, ferric bromide, and nitrate. M1g2 iron, inorganic iron salts such as ferrous nitrate, and ferric salts of ethylenediaminetetraacetic acid, ■-hydroxyethylidene-1,1-diphosphonic acid ferric acid, l-
ferrous hydroxyethylidene-1,1-diphosphonic acid,
Ferrous ethylenediaminetetraacetate, ferric diethylenetriaminepentaacetate, ferrous salt of diethylenetriaminepentaacetate,
Ferric citrate, ferrous citrate, ferric ethylenediaminetetramethylenephosphonate, ferrous ethylenediaminetetramethylenephosphonate, ferric nitrilotrimethylenephosphonate, ferric nitrilotriacetate, ferrous nitrilotriacetate, etc. Examples include organic acid iron salts. These organic acid iron salts, even in free acid form, include sodium salts, potassium salts, ammonium salts, tium salts, and alkylammonium salts (triethanolammonium salts, trimethylammonium salts, tetramethylammonium salts, etc.).
But that's fine. These soluble iron salts must be present in the stabilizing solution at least 5
It is preferably used at a concentration of
-'mol/Q range, more preferably 12X
It ranges from 10-'' to 100×10-” mole/Q.

In addition, these soluble iron salts may be added to the stabilizing solution (tank solution) by adding them to the stabilizing solution replenisher, or they can be added to the stabilizing solution (tank solution) by being eluted from the sensitizing material in the stabilizing solution.
It may be added to the stabilizer solution (tank solution), or it may be added to the stabilizing solution (tank solution) by attaching it to the photosensitive material to be processed from the prebath and bringing it there.

In addition, in the present invention, ion exchange resin treatment is performed to reduce calcium ions and magnesium ions to 5 ppm.
The stabilizer described below may be used, or a method may be used in which the above-mentioned anti-piping agent or halogen ion-releasing compound is further added to the stabilizer.

The pn of the stabilizer is preferably in the range of 5.5 to 1O10.

The pHi adjuster that can be contained in the stabilizing solution may be any commonly known alkaline agent or acid agent.

The amount of stabilizer replenishment is preferably 0.1 to 50 times, particularly 0.5 to 30 times, the amount of prebath (bleach-fix solution) brought in per unit area of light-sensitive material from the viewpoint of rapid processing and retention of dye images. is preferred.

The number of stabilizing tanks in the stabilization treatment is preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1 from the viewpoint of desilvering performance and rapidity.

Next, preferred photosensitive materials to which the present invention is applied will be explained.

Silver halide grains preferably used in photosensitive materials include silver chloride and silver chlorobromide, and in particular, silver halide grains containing mainly silver chloride containing at least 80 mol% of silver chloride are preferably used, and more preferably. 90 mol% or more,
More particularly, those containing 95 mol% or more, and most preferably 99 mol% or more are used.

Processing a light-sensitive material using such a silver halide emulsion containing mainly silver chloride is a preferred embodiment of the present invention.

The silver halide emulsion mainly composed of silver chloride may contain silver bromide and/or silver iodide as a silver halide composition in addition to silver chloride. In this case, silver bromide is preferably 20 mol% or less, More preferably 10 mol% or less, even more preferably 3
When silver iodide is present, it is preferably 1 mol or less, more preferably 0.5 mol % or less, and most preferably zero. Such silver halide grains consisting mainly of silver chloride containing 80 mol% or more of silver chloride may be applied to at least one silver halide emulsion layer, but preferably to all silver halide emulsions! This applies to

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of the [1,Q, (l] plane to the [1,1, 1 layer plane) can be used. The crystal structure of the silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-layer type) in which the inside and outside are different.

Further, these silver halides may be of a type that forms a latent image mainly on the surface. Furthermore, tabular silver halide grains (JP-A-58-113934, Japanese Patent Application No. 59-17)
0070) can also be used. Also, Unexamined Japanese Patent Publication 1986
-26837, 64-26838, 64-77
Silver halides described in No. 047 and the like can be used.

Further, the silver halide grains may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method.

Alternatively, for example, a method may be used in which seed particles are produced by an acidic method and further grown by an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, the pH% (p/1g) in the reaction vessel is controlled, and an amount commensurate with the growth rate of silver halide grains is controlled, for example, as described in JP-A No. 54-48521. It is preferable to implant and mix silver ions and halide ions sequentially and simultaneously.

The silver halide emulsion layer of the light-sensitive material processed according to the present invention contains color couplers. These color couplers react with color developer oxidation products to form non-diffusible dyes. Color couplers are preferably incorporated in non-diffusive form in or closely adjacent to the photosensitive layer.

Thus, the red-sensitive layer may contain, for example, a non-diffusing color coupler, typically phenolic or a-
It can contain natofur-based Kagura. The green-sensitive layer may contain, for example, at least one non-diffusive color coupler which produces a magenta partial color image, usually a 5-pyrazolone color coupler and a pyrazolotriazole.

The blue-sensitive layer may contain, for example, at least one non-diffusive color coupler, generally a color coupler having an open-chain ketomethylene group, which produces a yellow color image. Color couplers can be, for example, 6.4 or 2 equivalent couplers.

In the present invention, 2-equivalent couplers are particularly preferred.

Suitable couplers are disclosed, for example, in the following publications:
Agfa research report (Miteilung Inaus)
den Forschungslaboratory
nclet Agfa), Leh7 Erkusen/Munich (Leverkusen/ Munchen)
, Vol. m, p, 111 (1961), WPelz, "Color Couppler J"; LVenkataraman, "The Chemistry of Synthetic Dive J"
eChemistry of 5ynthetic D
yes), Vol. 4.341-387, Academic Press, “The
Theory of the Photographic Process”
(The Theory of the Photo
rapicProcess), 4th edition, 353-36
Page 2: and Research Disclosure (Rosea
rch Discclosure) No.

17643, Section ■.

In the present invention, in particular, JP-A-63-106655
Magenta couplers represented by the general formula CM-1) as described in No. 63-106655, p. 26 (Specific examples of these magenta couplers include No. 1-No. 77 described in Shika No. 63-106655, p. 29 to 34). ) same <3
General formula (C-1) or (C-11) described on page 4
) (Specific examples of cyan couplers include (c'-
1-(c′-82), (c#-t)-(c”-36)
), the high-speed yellow couplers described on page 20 of the same specification (specific examples of cyan couplers include (Y'-1) to (Y'-3) described on pages 21 to 26 of the same specification),
9)) is preferably used from the viewpoint of the desired effect of the present invention.

When a nitrogen-containing heterocyclic mercapto compound is used in a light-sensitive material containing a silver chloride-based emulsion, it not only achieves the desired effects of the present invention, but also prevents the bleach-fixing solution from mixing with the color developer. This can be cited as a more preferred embodiment of the present invention because it has the additional effect of reducing the resulting influence on the visual field immersion performance to an extremely small value of ρ.

Specific examples of these nitrogen-containing heterocyclic mercapto compounds include (
Examples include 1'-1) to (E'-87).

Silver halide emulsions based on silver chloride may be prepared by conventional methods (eg, single or double flow with constant or accelerated flow of material). I) Particularly preferred is the double inflow adjustment method while adjusting Ag; see Research Disclosure No. 17643, Sections I and ■.

Silver chloride-based emulsions can be chemically sensitized. Particularly preferred are sulfur-containing compounds such as allyl isothiocyanate, allylthiourea or thiosulfate. Reducing agents can also be used as chemical sensitizers and are described, for example, in Belly Patent Nos. 493,464 and 568,
687, and polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, such as for example diethylenetriamine according to Belgian Patent No. 547.323.

Noble metals and precious metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers.

This chemical sensitization method has been used in the Veitschrift Fair and Photography (Z, Wiss).
, Photo, ) 46.65-72 (1951) by R. Koslovsky; and the above-mentioned Research Disclosure No.

17643, see also Section ■.

Silver chloride-based emulsions are prepared using optically known methods such as common polymethine dyes such as neutro/anines, basic or acidic carbocyanines, rhodacyanines, hexyanines, styryl dyes, oxonols and the like.
Can be sensitized: F.M. Hammer (F, M,
Hamer)'s "The Cyanine Dive and Related Compounds"
yes ancl related cornpoun
ds) (1964) Jllmanns En
zyklpadie dertechnischen
Chemie) 4th edition, volume 18, page 431 and subsequent editions,
See also Research Disclosure No. 17643, Section ■.

Conventional antifoggants and stabilizers can be used in silver chloride-based emulsions. Azaindenes are particularly suitable stabilizers, with tetra- and pentaazaindene being preferred;
Particularly preferred are those substituted with a hydroquinol group or an amino group. Compounds of this type are for example Birr
Thesis, Veitschrift Fair Bissenjaftliche Fotografie (Z, Wiss, Photo
) 47.1952, p. 2-58, and the above-mentioned Research Disclosure No. 17643, Section ■.

The components of the photosensitive material can be incorporated by conventional known methods; for example, U.S. Pat. No. 2,322,027;
See No. 2,533,514, No. 3,689,271, No. 3,764,336 and No. 3,765,897.

Components of the light-sensitive material, such as couplers and UV absorbers, can also be contained in charged latex form: DE 2,541,274 and European Patent Comp.
See No. t 14,924. The components can also be immobilized in photosensitive materials as polymers; for example, DE 2,044,992, US Pat. No. 3,37Q;
See No. 952 and No. 4,080,211.

Although ordinary supports can be used as the support for the photosensitive material, reflective supports such as paper supports are most suitable in the present invention, and these include, for example, polyolefin,
In particular they can be coated with polyethylene or polypropylene; in this regard see Research Disclosure No. 17643, supra, section VVI.

If the photosensitive material contains a coupler and is processed using the so-called internal development method, it can be used as color paperback negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, or reversal. It can be applied to any photosensitive material such as color paper, but most preferably it can be applied to color paper mainly containing silver chloride.

〔Example〕

Example 1 Each layer having the structure shown below was coated on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the first layer side of the other side, and a multilayer silver halide layer was formed. A color photographic material (1) was prepared. The coating solution was prepared as follows.

1st layer coating liquid Yellow Cobra (Y-1) 26.7g, dye image stabilizer (ST-1) lo, Og, (ST-2)
Ethyl acetate 60+++Q was added to and dissolved in 0.67 g of 6.67 g additive (HQ-1) and 6.67 g of high boiling point organic solvent (DNP), and this solution was mixed with 7 mff of 20% surfactant (SU-1). A yellow coupler dispersion was prepared by emulsifying and dispersing the mixture in a 10% gelatin aqueous solution 220aII2 using an ultrasonic homogenizer. This dispersion was mixed into a blue-sensitive silver halide emulsion (
(containing 10 g of silver) to prepare a first layer coating solution.

The second to seventh layer coating solutions are also the same as the first layer coating solution. T I T I H ~ 1 [Preparation method of blue-sensitive silver halide emulsion] The following (liquid A) and (liquid B) were added to a 2% aqueous gelatin solution (10,100 O) kept at 40°C at p/Ig-6.5, pH -3.0, and simultaneously added over 30 minutes, and further the following (liquid C) and (
Solution D) was simultaneously added over 180 minutes while controlling pAg to -7.3 and pI (-5.5).

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

Solution CA) Sodium chloride 3.42g Potassium bromide 0.03g Add water and make 200 mQ (Liquid B) Add silver nitrate 10g water and add 200m12 (Liquid C) Sodium chloride 102.7g Potassium bromide 1.0g Add water A monodisperse cubic emulsion EMP2 having a 600+n12 silver chloride content of 99.5 mol % was obtained.

For EMP-2, the following compound was used at 120°C at 55°C.
Green-sensitive silver halide emulsion (EmB) after separation chemical ripening
I got it.

Sodium thiosulfate 1.5n+g1 mol Ag
X Chloroauric acid 1.0 mg/mol A
gX stabilizer SB -55x 10-'+=4/
-E-L AgX sensitizing dye D-24XlO-' 1 mol AgX [Preparation method of red-sensitive silver halide emulsion] Addition time of (Liquid A) and (Liquid B) and (Liquid C) and (Liquid D) A monodispersed cubic emulsion EMP with an average grain size of 0.50 μm, coefficient of variation (σ/r) = 0.08, and silver chloride content of 99.5 mol% was prepared in the same manner as EMP-1 except that the addition time was changed. −
I got 3.

/ EMP-3 was chemically ripened for 90 minutes at 60°C using the following compound to form a red-sensitive silver halide emulsion (EmC).
Get it.

Sodium thiosulfate 1.8 mg 1 mol 1 mol Auric acid 2.0 mg 1 mol AgX
(Liquid D) Add 300g of silver nitrate to water. After adding 600+nQ, desalt using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mix with an aqueous gelatin solution to obtain an average particle size. Diameter 0.85/J lll
A monodisperse cubic emulsion EMP-1 having a coefficient of variation (e/r) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

The above emulsion EMP-1 was chemically ripened for 90 minutes at 50°C using the following compound, and a blue-sensitive silver halide emulsion (E
mA) was obtained.

Sodium thioWL 0.8 mg 1 mol 1 mol A gold rdi 0.5 mg/
% AgX Stabilizer SB 5 5x 10”
”mol/mol AEX sensitizing dye D l 5X
10-'mo41 mol Ag
The average particle size was 0.4 in the same manner as EMP-1 except for changing the addition time of liquid) and the addition time of (liquid C) and (liquid D).
3 μm 1 coefficient of variation (σ/r ) = 0.08. After exposing this sample to light according to a conventional method, it was processed using the following processing solution.

Processing process ()) Color development 35.0±0.3°C (2) Bleaching 35.0±0.5°
C(3) Fixation 11(
4) Stable (3 tank cascade) 30~34°
C (5) Drying 60-80°
C (Color developing tank liquid) Triethanolamine 10g Ethylene glycol 1g N,N-diethylhydroxylamine 3.6g Hydrazinodiacetic acid 5.0g Potassium bromide
20 Potassium chloride
2.5g diethylenetriaminepentaacetic acid 5g potassium sulfite 5. OX
10-'mol color developing crude drug (3-methyl-4-amine-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate) 5.5 g 45 seconds 20 seconds 20 seconds 90 seconds 30 seconds Processing process stabilizer SB-5 6X 10-' mol 1 mol Ag , 10.

(Color developer replenisher) Triethanolamine
1
4.0g ethylene glycol 8.0
gN,N-diethylhydroxylamine 5ghydrazinodiacetic acid 7.5gpotassium bromide 8mgpotassium chloride 0.3gdiethylenetriaminepentaacetic acid 7.5gpotassium sulfite
7. OX 10-'Molar color developing agent (3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate) 8g potassium carbonate
30 g potassium bicarbonate
Add 1 g of water to bring the total volume to 1Q, and adjust the pH to 10.40 with potassium hydroxide or sulfuric acid.

5 g 5 g Potassium hydroxide or Ii, L; (JIJfl (bleach tank liquid) 1.3-propylenediaminetetraacetic acid ferric ammonium 0.32 mol ethylenediaminetetraacetic acid disodium 10 g ammonium bromide 100 g glacial acetic acid
40 g ammonium nitrate
Add 40 g water to make 14 and adjust pH to 4.5 using ammonia water.

(Bleach replenisher) 1.3-Propylenediaminetetraacetic acid Ferric ammonium 0.35 mole Ethylenediaminetetraacetic acid 2 Sodium ammonium bromide Glacial acetic acid Ammonium nitrate Add water to make 112 g 120 g 68.9 g 80 g Ammonia water Adjust the pH to 3.5 using a

(Fixer tank fluid and fixer replenisher) Ammonium thiosulfate 180 g Ammonium sulfite 20 g Urea
1g imidazole
4g ethylenediaminetetraacetic acid disodium 1g ammonium thiocyanate 1
Add 50g of water to make 112, and use ammonia water to make p
Adjust to H7.5.

(Stable tank fluid and replenishment fluid) Ortho-phenylphenol O, 1g Ubitex (manufactured by Ciba Geigy) 1.0g ZnSO4
・7HJ O, 1g ammonium sulfite (40% solution) 5.0m (11-
Hydroxyethylidene-1,130g diphosphonic acid (6
0% solution) Ethylenediaminetetraacetic acid 1.5g Water-soluble surfactant Listed in Table 1 Adjust pH to 7.8 with aqueous ammonia or sulfuric acid, and adjust to IQ with water.

Running processing was performed using the prepared color paper and processing solution.

In the running process, the automatic processor is filled with the above color developer tank solution, as well as the bleach-fix tank solution and the stabilization tank solution, and the above color developer replenisher and bleach are added every 3 minutes while processing the color paper sample. The fixing replenisher and stable replenisher were replenished through the fixing pump.

Further, in the stabilizing bath, in order to adhere the stabilizing liquid and the ion exchange resin or adsorbent, a small bag (shaped like a tea bag) containing the ion exchange resin or the adsorbent was placed in a part of the filter of the stabilizing bath.

The amount of replenishment to the color development tank is 1m of color paper.
The amount of replenishment to the bleach-fix tank was 220 m4 of bleach-fix replenisher per In'', and the amount of replenishment to the stabilization tank was 250+nQ of stable replenisher per 1 m2.

In the running process, continuous FC processing of Sail 05R was performed per day until the amount of color developer replenished into the color developer tank solution became three times the volume of the color developer tank solution. Note that 1R means that the color replenisher is replenished to the capacity of the color developing tank.

After continuous processing, the spectral reflection density at 640 nrrl of the unexposed area was measured to evaluate the stain. In addition, the tendency of crystal precipitation on the wall of the roller tank in the stabilizing bath was evaluated.

■ Roller: No precipitates at all on the tank wall. ○ Roller: A small amount of precipitate is observed on the tank wall. 8. Roller: There is a small amount of precipitate on the tank wall.

X There is a large amount of precipitates on the roller and tank walls.

XX Roller There was a large amount of precipitate on the tank wall, and it settled on the bottom of the tank.

The above results are shown in Table 1.

As is clear from Table 1, the surface tension of the stabilizer is between 15 and 6.
By adding an appropriate amount of the water-soluble surfactant of the present invention to the stabilizing solution and further bringing the adsorbent into contact with the stabilizing solution, the surface of the roller tank in the stain stabilizing bath in the unexposed area is It can be seen that the crystal precipitation properties are significantly improved.

In addition, the water-soluble surfactant of the present invention can be used as Exemplary Compound I-6,
Similar effects were confirmed even when changing to 12, 15, 16, 18, 19, I[-9, ■-10. Furthermore, when a large amount of the water-soluble surfactant of the present invention was added to the stabilizing solution to make the surface tension of the stabilizing solution 13 dyne/cm, the edge portions of the photosensitive material were destroyed.

Example 2 Exemplary compound ■-17 was used as a water-soluble surfactant to be added to the stabilizing solution, and the surface tension of the stabilizing solution was adjusted to 20 clyn/c.
The experiment was conducted in the same manner as in Example 1, except that the type of ion exchange resin or adsorbent to be brought into contact with the stabilizing solution in the stabilizing bath is shown in Table 2. The crystal precipitation properties were evaluated. The results are shown in Table 2.

(For the amount of water-soluble surfactant added, the surface tension of the stabilizing liquid will be the value shown in Table 1.) As is clear from Table 2, using the water-soluble surfactant of the present invention, It can be seen that by bringing the resin or adsorbent into contact with the stabilizing solution, staining in unexposed areas and crystal precipitation on the wall of the roller tank in the stabilizing bath are significantly improved.

In addition, as a water-soluble surfactant, I-5,6゜12 1
4 16, 18.19. It-3, 4, 9, 10, 1
Using 3°14, the surface force of the stabilizing liquid is 20 dyne/cm.
A similar effect was confirmed when

Example 3 The same experiment as in Example 1 was conducted except that the adsorbent contacted with the stabilizing solution, the water-soluble surfactant added to the stabilizing solution, and the amount of stabilizing solution replenishment were changed to the amounts shown in Table 3. Two.

As is clear from Table 3, by adding the water-soluble surfactant of the present invention and bringing the adsorbent into contact with the stabilizing liquid,
It can be seen that even when the amount of stabilizer replenishment is small, staining in unexposed areas and crystal precipitation on the wall surface of the roller tank in the stabilizer are significantly reduced.

In addition, as water-soluble surfactants, I-6, 12, 14°16, 18.19. II-4, 9, 10, 13, 1
Similar effects were confirmed when the surface tension of the stabilizing solution used in Example 4 was set to 20 dyne/cm.

Embodiment 4 FIG. 1 is a sectional view showing an example of an automatic developing machine used in the present invention, and FIG. 2 is a plan view of the automatic developing machine.

In FIG. 1, reference numeral "] indicates a developing machine main body, and the front side of this developing machine main body 1 is provided with a supply section 4 for supplying an undeveloped negative color film 2 or a color paper positive light sensitive material 3, and a rear Processed photosensitive material 2 on the side,
3 are respectively provided.

Between the supply section 4 and the take-out section 5, that is, the developing machine main body 1
Inside, there are a developer tank 6, a bleach solution tank 7, a fixer tank 8, and a stabilizer tank 9.
．． 11 and a drying section 12 are provided.

The developer tank 6, the bleach tank 7, the fixer tank 8, the first stabilizer tank 9, 10, and the second stabilizer tank 11 are constructed as shown in FIG. That is, the developer tank 6 is the burr developer tank 6.
It consists of a positive developer tank 6b and a positive developer tank 6b, each of which is filled with a dedicated developer.

The negative photosensitive material 2 is processed separately in a negative developer tank 6a, and the positive photosensitive material 3 is processed separately in a positive developer tank 6b, so that photographic performance can be maximized.

The processing tanks located after the developer tank 6, that is, the bleaching solution tanks 7a and 7b and the fixing solution tanks 8a and 8b, are filled with a bleaching solution and a fixing solution having the same composition, respectively. or,
For stabilizer baths, 9a, 10a, lla and 9b
10b can be filled with stabilizing liquids having different compositions, and 9a, ]Oa, lla, 9b, lO
Stabilizing liquids having the same composition may be filled in all of b. In this way, the stabilization treatment of photosensitive materials uses a stabilizing solution instead of washing water, so water is not required, and there is no need to provide a drain pipe, so the installation location cannot be specified.

And, as shown in FIG. 2, a first stabilizing liquid tank 9a.

Cascade piping 14, 15, and 16 are provided between 10a and 10a, 10a and lla, and 9b and lOb, and when the replenisher replenished in the stabilizing liquid tanks 11a and 10b overflows, the first stabilizing liquid tank in the previous stage] It flows into Oa, 9a and 9b. This makes it possible to further use the overflow stabilizing solution, thereby increasing the efficiency of the stabilizing process.

Regarding replenishers, in the case of color developer replenishers, separate replenishers are used for negative and positive development, and for bleach replenisher, fixing replenisher, and stable replenisher, the same composition is used for both negative and positive development. Using a replenisher A color negative film sample 1 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

1st layer; Anti-haline layer (HC) Black colloidal silver 0.15 UV absorber (UV~1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling point solvent (○i L -1) 0.20 ///
(Oi L-2) ” 0.20 Gelatin 1.6 2nd layer; Intermediate layer (IL-1) Gelatin 1.3 3rd layer;
Low-sensitivity red-sensitive emulsion layer (R-L) silver bromide emulsion (Em-
]) 0.4tt (Em-2)
0.3 sensitizing dye (S-1) 3.2X 1
0-' (mol/silver 1 mol)'' (S 2 ): L2
X 10-'(tt)'/(S-3)0
．． 2x 10 (//) uncoupler (C-
1) 0.50// (C-2)
0.13 colored cyan coupler (C
C-1) DIR compound (D-1) tt (D2) High-boiling point solvent (OiL-1) Additive (5C-1) Gelatin vg4 layer; High sensitivity red-sensitive emulsion layer (R-H) Silver iodobromide Emulsion (Em-3) Sensitizing dye (s -1) 1.7x lO-' (mol/silver/
/ (S-2)1.6X10-'(//// (S
-3)0. lXl0-'(//Cyan coupler (C-2
) Colored cyan coupler (CC-1) DIR compound (D-2) High boiling point solvent (○1L-1) Additive (SC-1) Gelatin 5th layer; Intermediate layer (IL-2) Gelatin 6th layer; Low Sensitivity Green-sensitive emulsion layer ((, -1) 0.07 0.006 0.0I O155 0,003 1,0 0,9 1 mol) 0.23 0.03 0.02 0.25 0.003 1. 0 0°8 Silver iodobromide emulsion (Em-1) 0.6tt
(Em 2) (12 sensitizing dye (S-4) 6.7X 10-' (mol/silver 1 mol)/
/ (S-5)0.8XIO-'(//) Magenta coupler (M-1) 0.17//
(M-2) 0.43 Colored magenta coupler (CM-1) 0.10 DIR compound (D-3) 0.02 High boiling point solvent (Oi L-2) 0.70 Additive (
'S C-1) 0.003 Gelatin l・0 7th layer;
High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (E m
-3) 0.9 sensitizing dye (S -6) 1
．． lX 10-' (mol/silver 1 mol) sensitizing dye (S-
7)2. OX 10-'(// )// (S
-8) O13X10-' (tt) Magenta coupler (M-1) 0.03//
(M-2) 0.13 colored magenta coupler (CM-1) 0.04 DIR compound (D-
3) 0.004 high boiling point solvent (OiL
-2) Additive (sc-1) Gelatin 8th layer; Yellow filter layer (yc) Yellow colloidal silver additive (H5-1) Additive (H5-2) Additive (SC-2) High boiling point solvent (OiL -2) Gelatin 9th layer: Low-speed blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) tt (Em 2) Sensitizing dye (S-9) 5.8X 10-' (mol /Silver yellow coupler (Y-1) tt (Y2) DIR compound (D-1) tt (D-2) High boiling point solvent (○1L-2) Additive (SC-1) 0.35 0.003 1. 0 0.1 0.07 0.07 0.12 0.15 1.0 0.25 0.25 mol) 0.60 0.32 0.003 [1006 0,18 0,004 Gelatin No. 10111, high sensitivity Blue-sensitive emulsion layer (B-H) Silver iodobromide (Em-4) Sensitizing dye (S-10)3. OX 10-' (mol/silver) (S 11) 1.2X 10-' (//Yellow coupler (Y-1) tt (Y2) High boiling point solvent (○1L-2) Additive (SC-1) Gelatin $11 layer; 1st protective layer (PRO-1) Silver iodobromide (Em-5) Ultraviolet absorber (UV-1) tt (UV-2) Additive (H5-1) Additive (H5-2) High boiling point solvent (OiL-1) // (○1L-3) Gelatin 12th layer: 2nd protective J layer (PRO-2) 1.3 0.5 1 mol) 0.18 0.10 0.05 0.002 1.0 0.3 0.07 0.1 0.2 0.1 0.07 0.07 0.8 Alkali-soluble matting agent 0.13 (average particle size 2 μm) Polymethyl methacrylate 0.02 ( Average particle size 3 μm) Slip agent (WAX-1) 0.04
Charge control agent (S LJ-1) 0.
004// (SO-2) 0.
02 Gelatin 0.5 Furthermore,
In addition to the above composition, each layer contains a coating aid SU4, a dispersion aid 5U-3, a hardening agent H-1. H-2 stabilizer 5T-1, preservative DI-1, antifoggant AF-1, AF-2, dye A
1-1 and Al-2 were added as appropriate.

The emulsions used in the above samples are as follows.

All of them are monodisperse emulsions of internal high locus type.

Em-1: Average Ag + content 7.5 mol% octahedral Em
-3: Average Ag Em 4: Average Ag Em 5: Average Ag ■Content 8.0 mol% Octahedral grain size 0.84 μm Process content 8.5 mol% Octahedral grain size 1.02 μm L content 2. 0 mol% Octahedral grain size 0.55 μm Em-2: Average Agr content 25 mol% Octahedral CM Shiri V-1 (IHV n) I [(CH.

CH5(hcHz)sccH2sO2(CHz)i]1
N(CH2)is○, K(alkanol XC) NaO,S CC00C,H,.

CH2C00CsH++ C2H.

(CH2) 1503° (CH2), 50. H (CH2)lsO3゜ C,H.

(CHri4SO3e mixture (2:3) A J1 ○ il -2 T il ■ AX MW: 30.000 F (Color paper processing) MW: 9,000 The color film prepared as above and in Example 1 The color paper samples used were exposed to light in a conventional manner and then subjected to the following treatments.

(The amount of replenishment is the value per 1 m2 of photosensitive material.

<Color developing tank liquid for color negatives> Potassium carbonate Sodium bicarbonate Potassium sulfite Sodium bromide Potassium iodide Hydroxylamine sulfate Sodium chloride 4-aminol 3-Methyl-N-ethyl-N-(β-hydroquinlethyl) Aniline sulfate 0g 2.5g 3, Og i, 2g 0.6mg 2.5g 0.6g 4.6g Diethylenetriaminepentavinegar D 3.0g Potassium hydroxide 1.2g Add water to make 1Q, and add potassium hydroxide or 20% sulfuric acid. using pH
Adjust to 10.01.

Color developer replenisher for color negatives> Potassium carbonate 40 g Sodium bicarbonate 3.0 g Potassium sulfite 7.0 g Sodium bromide
0.5 g hydroquinlamine sulfate 3.1 g sodium chloride
0.6g 4-amino-3-methyl-N-ethyl-N(β-hydroquinlethyl) Aniline sulfate 6.0g diethylenetriaminepentaacetic acid R3, Og Potassium hydroxide 2.0g Add water to make 1Q, potassium hydroxide or 20%FAM'c
pH 10,121: VF4%.

Color development tank liquid for color paper> Diethylene glycol 10 g Potassium bromide
0.01 g potassium chloride
2.3g potassium sulfite (50% solution)
0.5 mQ color developing agent (3-methyl-
4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate) 7.0 g Diethylhydroxylamine (85%) 5.0 g Triethanolamine 10.0 g Potassium carbonate 30 g Diethylenetriamine Sodium acetate salt 2. Og fluorescent whitening Qi Batiba Geigy Uvitefux CK)
2.0 g of water was added to make it iff, and the pH was adjusted to 0.15 with sodium hydroxide or sulfuric acid.

<Color developer replenisher for color paper> Diethylene glycol 10 g Potassium chloride 3.0 g Potassium sulfite (50% solution) 0.5 mff Color developer (3-methyl-4-amino N-ethyl-N-(β-
(methanesulfonamidoethyl)-aniline sulfate)
8.0 g diethylhydroquinolamine (85%
) 7.0g triethanolamine
10.0g potassium carbonate 3
0 g diethylenetriaminepentaacetic acid sodium salt 2.0 g optical brightener (Iupitefx (J) manufactured by Ciba Geigy)
2.5 g of water was added to give Ic, and the pH was adjusted to 10°40 with sodium hydroxide or sulfuric acid.

<Bleach tank liquid> 1.3-Propylenediaminetetraacetic acid Ferric ammonium 0.32 mol Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 100 g Glacial acetic acid
Add 40 g ammonium nitrate 40 g water to make IQ, and adjust pH to 4.5 using aqueous ammonia.

Bleach replenisher> 1.3-Propylenediaminetetraacetic acid Ferric ammonium 0.35 mol Ethylenediaminetetraacetic acid disodium 2g Ammonium bromide 120g Glacial acetic acid
68.9g ammonium nitrate
Add 80 g water to make up to 1Q, and adjust the pH to 3.5 using aqueous ammonia.

Fixer tank fluid and fixer replenisher> Ammonium thiosulfate 180g Ammonium sulfite 20g Urea
1g imidazole
4g ethylenediaminetetraacetic acid disodium 1g ammonium thiocyanate 1
Add 50g of water to make 1 (1), and use ammonia water to make p
Adjust to H7.5.

<Stable tank liquid and stable replenisher> 1.2-penftyanolin-3-one 0.2
g Water-soluble surfactant Listed in Table 4 Add water to make IQ, and use potassium hydroxide ratio and 50% sulfuric acid to make p
H was adjusted to 7.0.

Load the above processing solution into the automatic developing machine shown in Figure 1.2,
Furthermore, in the stabilizing bath for paper (Fig. 1.2 9b, 10b), in order to bring the stabilizing solution into contact with the ion exchange resin or absorbent, a small bag (tea bag) containing the ion exchange resin or absorbent is placed in the filter section of the stabilizing bath. 2.0 m'' of the color negative film and 12 m2 of the color paper were processed per day, and continuous running was performed for 30 days.

We also tried a method in which the overflow of the negative stabilizing solution was poured into the paper stabilizing solution using the cascade piping 13 shown in FIG.

After the continuous processing, the spectral reflection density at 640 nm of the unexposed area of the processed color paper was measured to evaluate residual color stain. In addition, the following evaluation criteria were used to evaluate the ability of crystals to be deposited on the rollers and tank walls in the paper stabilizing bath.

The results are shown in Table 4.

@ Roller There is no precipitate on the tank wall O Roller There is a small amount of precipitate on the tank wall Roller There is a small amount of precipitate on the tank wall.

× Roller: There is a large amount of precipitate on the tank wall.

×× Roller There was a large amount of precipitate on the tank wall, and it settled on the tank bottom.

△ The same experiment as in Example 4 was conducted except that the water-soluble surfactant added to the stabilizer and the amount of stabilizer replenished for paper processing were changed as shown in Table 4. The tendency of crystal precipitation on the wall surface of the roller tank in the stabilizing bath was evaluated.

As is clear from Table 4, the surface tension of the stabilizer is 60dy.
Add an appropriate amount of the water-soluble surfactant of the present invention to the stabilizing solution so that the concentration is below ne/cm, bring the ion exchange resin or absorbent into contact with the paper stabilizing solution, and then overflow from the negative stabilizing bath to the paper stabilizing bath. It can be seen that by pouring the liquid, staining of the unexposed areas of the paper and crystal precipitation on the wall of the roller tank in the stabilizing bath are greatly improved.

In addition, the water-soluble surfactant of the present invention is exemplified by compound I-612.
,14,15,16,18,19,n-4,910,1
Similar effects were confirmed even when changing to 3 and 14.

Example 5 The same experiment as in Example 4 was carried out except that the ion exchange resin or adsorbent described in Example 2 was used to contact the paper stabilizing solution, and the stain of the unexposed part of the paper, the roller in the stabilizing bath, and the tank wall were carried out. As a result of evaluating the crystal precipitation property of
Good results similar to those in Example 3 were obtained.

Example 6 As is clear from Table 5, the water-soluble surfactant of the present invention was added to the stabilizing solution, the ion exchange resin was brought into contact with the stabilizing solution for paper, and the overflow was caused from the stabilizing bath for negatives to the stabilizing bath for paper. It can be seen that by pouring the liquid, even when the amount of replenishment of the stabilizing liquid for paper processing is small, the prevention of staining on the unexposed areas of the paper and crystal precipitation on the wall of the roller tank in the stabilizing bath is greatly improved. .

〔Effect of the invention〕

The present invention provides a silver halide color photographic light-sensitive material that prevents crystal precipitation on stain processing tanks and rollers caused by pigments, dyes, etc. remaining in color photographic paper, and achieves rapid processing and low replenishment. We were able to provide a processing method for this.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing an example of an automatic developing machine used in the present invention, and FIG. 2 is a plan view of the same. 1. Developing machine body 2: Non-gauss photosensitive material 3: Positive photosensitive material 4: Supply section 5: Take-out section 6: Developing solution tank 7: Bleach solution tank 8: Fixing solution tank 9, 10.11: Stabilizing solution tank

Claims (2)

[Claims] (1) After imagewise exposure of a silver halide color photographic material in which the average silver chloride ratio of the silver halide emulsion coated on a support is 80 mol % or more, color development processing is performed, followed by bleaching processing, fixing processing and In the stabilizing treatment method, a water-soluble surfactant is contained in the stabilizing solution so that the surface tension of the stabilizing solution is 15 to 60 dyne/cm, and an ion exchange resin or an adsorbent is brought into contact with the stabilizing bath. A method for processing a silver halide color photographic light-sensitive material. (2) The method for processing a silver halide color photographic material according to claim 1, wherein the water-soluble surfactant according to claim 1 has the following general formula [I] or [II]. General formula [I] R-O■A■_n■B■_mD [In the formula, R is an alkyl group having 4 to 25 carbon atoms that may have a linear or branched substituent, or ▲ mathematical formula, chemical formula, There are tables, etc. ▼ or represents a hydrogen atom. (However, R_1 and R_2 each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may have a substituent, and 1 represents an integer of 0 to 4.) n and m are each 0 or 1 to 4. It represents an integer of 200, but it cannot be 0 at the same time. A and B each represent ▲a mathematical formula, a chemical formula, a table, etc.▼, and may be the same or different. (However, n_1, m_1 and l_1 are 0 and 1, respectively.
, 2 or 3, but n_1, m_1, l_1 are 0 at the same time
It won't be. ) D represents a hydrogen atom, -SO_3H or -PO_3H. M here represents a hydrogen atom, an alkali metal or ammonium. ] General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_3 is a hydrogen atom, hydroxy group, lower alkyl group, alkoxy group, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is ▲ Mathematical formula, There are chemical formulas, tables, etc. Represents ▼. R_4,
R_5 and R_6 each represent a lower alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl, etc.);
5 and R_6 may be the same or different. l_1 to l_3 each represent an integer of 0 or 1 to 4,
p, q_1, and q_2 each represent an integer from 1 to 15. ] (3) A silver halide color photographic light-sensitive material in which the average silver iodide ratio of the silver halide emulsion coated on the support is 2 mol % or more, and silver chloride in the silver halide emulsion coated on the support. In a method of mixing and processing silver halide color photographic light-sensitive materials having a ratio of 80 mol % or more using at least one same replenisher in a processing bath other than a color developing bath, the former silver halide color photographic light-sensitive material 3. The method for processing a silver halide color photographic material according to claim 1, wherein part or all of the overflow liquid is poured into a stabilizing bath for processing.